Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2~78~11
In the production of chrome leather~, as is usual ~in
practice, pelt material is tanned with commercially
available chromium(III) salts after pickling. After
mechanical dewatering and splitting, if appropriate, the
resulting wet-blue i8 brought to the de~ired thickne~s by
shaving.
In this case, large quantities of chromium-containing
shavings are obtained, which nowadays cause ecological
problems in disposal. The same applies to corresponding
trimming wastes.
To overcome this problem, it was propo~ed in US Patent
Specification 4,060,384 to pretan the pelt material
without chromium, ~o that the 3hrinking temperature of
the hides ri6es to 77 - 85C. The appropriately pretanned
hide material is then split (in the case of unsplit
pelts) and shaved, shavings being obtained which do not
contain chromium and are easy to dispose of. The hide
material thus pretreated mechanically is then chromium-
tanned in the conventional manner. This process is called
the wet-white process in practice.
Furthermore, for the pretanning claimed in US Patent
Specification 4,060,384, the following tanning substances
have, for example, been proposed in the meantime:
- aluminium compound~ (for example Leather
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Manufacturer 105 (1987) 12, 9~16, Leder- und
Hautemarkt (1985) 19, 28-35, JALCA 79 (1984) 6);
- aluminium compounds/titanium compounds (for example
EP-A 0,291,165, German Publi~hed Specification
3,903,499);
- glutaraldehyde or glutaraldehyde derivative~,
optionally in combination with resin/replacement
tanning agent (for example German Published Speci-
fication 3,935,879, JALCA 78 (1983) 174, LIRI
Research Bulletin No. 894 (1985), JALCA 74 (1979) 9,
288-300);
- replacement tanning agents based on bis
(4-hydroxyphenyl)-sulphone (for example
EP-A 428,481, Rev. Tech. Ind. Cuir 77 (1985) 5,
161-165);
- oxazolidines (for example Leather 188 [1986] 4531,
41-43)-
The chrome leathers produced with the aid of the sub-
Rtances described above markedly differ in the leather
character from conventionally chrome-tanned and shaved
leathers with respect to feel (see, for example, Da6
Leder 37 (1986) 12, 221-224), fullne~s, softness and
dyeability. As experience shows, ~uch serious deviations
in the property pattern are not tolerated by the leather
manufacturer and/or leather proce~or.
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To avoid such di~advantages in the ~urther processing, it
was proposed in the case of the aluminiu~ pretreatment
largely to remove the aluminium salts by washing after
shaving before the chrome-tanning (~ee Das Leder 38
(1987) 4, 71-75). This additional working step, however,
lead3 to a pollution of the effluent with aluminium
~alts, which is not unobjectionable from a toxicological
view.
It has now been found, ~urprisingly, that a pretreatment
can also be carried out with special condensation pro-
duct3 not havinq a ta_nina action, giving a substrate
which, without any problems, can be mechanically
dewatered and shaved or split and shaved. The hide
material pretreated in this way has, after appropriate
preservation, unlimited storage stability under condi-
tions usual in practice. The leather sub~equently result-
ing therefrom after chrome-tanning does not differ in its
application properties from conventionally chrome-tanned
and shaved leathers.
The invention thus relate~ to a process for producing
chrome leather, characterised in that the hide material
delimed, bated and pickled in the conventional manner is
pretreated in an aqueous liquor with a condensation
product not having a tanning action and, after mechanical
dewatering, is shaved or (in the ca~e of unsplit pelt
material) split and shaved and then chrome-tanned with
commercially available chromium(III) salts and after-
treated in the usual way. The usual aftertreatment in
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general comprises neutrali~ation, retanning, dyeing and
fat-liquoring.
The pretreatment agents used according to the invention
are condensation product~ of aromatic sulphonic acids
which do not contain any phenolic hydroxyl groups, for
example those of C6-C24-aromatics such as of naphthalene,
or of diaryl ethers, for example of the ditolyl ethers,
preferably of ~-naphthalenesulphonic acid, with form-
aldehyde. Aromatic sulphonic acids which are preferred
for the condensation contain 0.8 to 3 and preferably 1 to
2 sulphonic acid groups per molecule.
The preparation of the condensation products to be used
according to the invention is described below, taking
~-naphthalenesulphonic acid/formaldehyde as an example:
1.1 to 1.8 and preferably 1.4 to 1.5 mol of 100% strength
sulphuric acid can be used per mole of naphthalene. The
~ulphonation is as a rule carried out at temperatures
from 120 to 160 and preferably 140 to 150C; it is
usually complete within 1 to 3 hours. 0.4 to 0.8 and
preferably 0.55 to 0.65 mol of formaldehyde are added (in
most cases in the form of its aqueous solution). The
condensation can take place at temperatures from 95 to
120C and preferably 110 to 120C; it is as a rule
complete within 2 to 5 hour Finally, the product is
neutralised with alkali metal hydroxide solution to a pH
value from 5 to 8 and preferably from 6 to 6.5, or with
ammonia to a pH value from 2 to 5 and preferably from 3
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to 3.5. In a preferred embodiment, these products are
adjusted with 1 to 8 and preferably 3 to 4% by weight,
relative to condensation product, of C4-C~-dicarboxylic
acid (for example glutaric acid) to an acid number (mg of
ROH/g) from 20 to 60.
The condensation products used according to the invention
have no tanning action of their own (Bibliothek des
Leders [Leather Library}., Volume 3, page 65, Umschau~
Verlag, Frankfurt/Main, 1st edition 1985) in the sense of
a covalent collagen crosslinking, such as i8 achieved,
for example, by polyfunctional aldehydes and isocyanates,
or in the sense of a collagen crosslinking by hydrogen
bond formation with phenol-containing replacement/
vegetable tanning agents, or in the sense of a collagen
crosRlinking by the formation of complexes of mineral
tanning agents.
~y means of the treatment with the condensation products
used according to the invention, shrinkage temperatures
of less than 65C are achieved. At the same time, how-
ever, they effect an extremely strong dewatering of thehide materi.al on the samming machine and allow problem-
free mechanical shaving, without ~corching phenomena.
In this case, it proves to be particularly advantageous
that the flhaved thickness of the hide material thus
pretreated is the same as the thickness of the chrome-
tanned fini3hed leather and makes additional shaving.
superfluous.
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A further resulting advantage i5 that the time sequence
of this wet-white process largely correspond~ to the
production rhythm of conventional chrome leather produc-
tion.
In the process according to the invention, the pelt
material obtained by the conventional soaking and lLming
operation~ is delimed, bated and adjusted with organic
and/or inorganic acid~ to pH values from 2 to 6 and
preferably 2.5 to 4.~ (pickled) in the conventional
manner.
The pretreatment iæ then carried out with 3 to 15 and
preferably 4 to 8% by weight (relative to pelt weight) of
the abovementioned condensation products, relative to
solids content.
lS After mechanical dewatering, the hides thus pretreated
can be perfectly shaved or, in the case of unsplit pelts,
~plit and shaved.
The hides are then chrome-tanned with commercially
available chromium(III) salts and finished in the conven-
tional manner.
The finished leather~ obtained by the process according
to the invention show no differences in the property
pattern as compared with conventionally produced chrome
leathers. The leathers can be brilliantly dyed and are
therefore particularly ~uitable for producing high-grade
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aniline leather~ for proces~ing to give furniture
leathers, shoe upper leathers and garment leather~.
The shavings obtained by the process according to the
invention are chromium free and allow diverse possibil-
ities o~ disposal.
The condensation products u~ed according to the invention
can be used in the spray-dried form or as an aqueous
801utioll .
The condensation products used according to the invention
can also be used in combination with other tanning
substance~. The following may be mentioned as examples:
- inorganic aluminium compounds and/or titanium
compounds
- aldehydes
- oxazolidines
- compounds containing phenolic groups, and mixtures
of these substances.
The percentage data in the examples which follow relate
to the weight, unless otherwise stated.
The dilution ratios mentioned in the examples which
follow relate to parts by weight, the larger number
always denoting the parts of water.
The concentrations of the acids to be diluted correspond
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to the manner usual in practice: 85% strength formic
acid, 96~ strength ~ulphuric acid.
ExamPles
Preparation of the condensation product to be used
according to the invention
1 mol of naphthalene i~ ~ulphonated for 3 hour~ at 145C
with 1.43 mol of 100% strength ~ulphuric acid. The
sulphonation mixture iB allowed to cool slightly and is
aondensed for 3 hours at 115 - 117C with 0.64 mol of
formaldehyde which is u~ed in the form of its 30%
ctrength aqueous solution. The reaction mixture i~ then
allowed to cool to 80C/ and aqueous ammonia is then
added up to a pH value of 3.5. 4%, relative to the
resulting ammonium salt of the condensation product, of
glutaric acid is added to this solution, an acid number
of 35 thus being obtained. The product is preferably
spray-dried, but it can also be u~ed a~ a 40-60% strength
aqueous solution.
Example 1
Production of furniture leather
a) By the wet-white process
For producing furniture leather, 800 kg of cow-hide pelts
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(~plit to 2 mm) limed in the u~ual manner are first
washed in the tanning vessel with 100~ (relative to the
pelt weight; like all percentage data below) of water at
35C for 15 minutes. The liquor i~ drained off, and
deliming i8 then carried out without liquor with 1.3% of
ammonium chloride and 0.4~ of citric acid for 45 minutes,
80% of water at 35C is added, and pickling with 0.2% of
a commercially available bating agent (with 1500 tryptic
units) i6 carried out for 120 minutes (pH value of the
liquor 7.7). The cross-section of the pelts no longer
gives any red coloration with phenolphthalein. This iB
followed by washing with 100% of water at 25C and the
liquor is drained off except for a re~idual liquor of
about 50%. 5 minutes after the addition of 8% of common
~alt, 0.4% of formic acid (diluted with water 1:10) and,
after a further 10 minutes, 0.6% of sulphuric acid
(diluted with water 1:10) are added, and pickling is
carried out for 180 minute~ (pickling pH value 3.4).
5~ of the condensation product to be u~ed according to
the invention i8 then added to the pickling liquor. After
one hour, 1% of a commercially available ~ynthetic fat is
added, and tumbling i~ continued for 10 hours. The final
pH value i~ 3.4 and the final temperature is 31C.
After draining off the residual liquor, the wet-whites
are unloaded, sammed and, optionally after temporary
~torage for 24 hours, shaved to 1.0 mm thicknes~. Thi~
gives about 30 kg of chromium-free ~havings per 100 kg of
pelt used.
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300 kg of shaved wet-whites were treated in 250% (rela-
tive to shaved weight; like all percentage data below) of
water at 35C with 1% of a commercially available syn-
thetic fat and tumbled for 15 minutes. 0.5% of formic
acid (diluted with water 1:10) are then added, followed
after 45 minutes by 11.5% of a commercially available,
weakly organic-masked chromium(III) sulphate solution
with 15% of chromium(III) oxide and 40% basicity
(according to ~Schorlemmer) and, after a further 15
1~ minutes, by 3% of fat (see above). After a running time
of 60 minutes, 0.9% of sodium bicarbonate iB added in 3
portions at 30 minute intervals each, and running is
continued for 120 minutes (pH = 3.4). The liquor is
heated to 38C, and 4% of a commercially available
chromium-syntan complex (commercially available chromium-
containing synthetic retanning agent with 12% of
chromium(III) oxide~ iB added, 6% of a fat mixture of
natural and synthetic fats is added after a running time
of 15 minutes, and tanning is completed in 8 hours. The
residual liquor has a chromium(III) oxide content of
1.8 gtl, a final p~ value of 3.3 and a final temperature
of 35C. In the usual manner, the leather i8 then neutra-
lised to p~ 6.5, fat-liquored and finished via inter-
mediate drying.
b) according to chrome-tanning as usual in practice
The pelts (shaved thickness 2 mm) delimed, bated and
pickled in Example la) are treated in the pickling liquor
with 2.3% (relative to pelt weight, like all percentage
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data below) of a commercially available ~ynthetic fat
and, after 15 minutes, 9% of a commercially available,
weakly organic-masked chromium(III) ~ulphate solution
with 15~ of chromium(III) oxide and 40% basicity
(according to Schorlemmer)ic added. After a runniny time
of 90 minutes, 0.35~ of magnesium oxide i8 added, and
tumbling i8 continued for 10 hours. The final pH value i8
3.8 and the final temperature i~ 38C. The chromium(III3
oxide content of the residual liquor iq 5.9 g/l.
The re6ulting wet-blue~ (with about 3.8% of chromium(III)
oxide, rela~ive to water-free wet-blue) are sammed and
shaved to 1.0 mm thickne~s. The shaved wet-blue~ have the
~ame chromium(III) oxide content as the wet-white~
chrome-tanned in Example la) after shaving. Per 100 kg of
pelt used, this give~ about 28 kg of chrome shavings with
about 3.8% of chromium(III) oxide, relative to water-free
chrome shavings. In the usual manner, the leather is then
neutralised to pH 6.5, fatted and finished via inter-
mediate drying.
The following table compares the chromium emis~ion~ of
the two proce~e~.
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.,~
--
o o
U
o ~
o W
~J~
'~ ~ D~
O ~ ~ O ~D
Ll o ~ N
U U el~
111 ~1 a~
~ .Y
.,1 ~ ~ ~ _
~ C ~ 1
.C ~ U O ~ ~
~r
U~
~0
O
U _
--I ~ -- O
~ ~ IJ
.r~ O
O
.C
~O~ U
U~
Q~
U _~
O
rl
U~ ~ _
I O O
x (a -- ~D
W
o
.Y
O
O .
Le A 28 634 - 12 -
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Example 2
Production of furniture leather
For producing furniture leather, the wet-white leather
produced in Example la) is Rammed and shaved. 100 kg of
shaved wet~whites are treated in 250% of water trelative
to the shaved weight; like all percentage data below)
with 1.5% of a commercially available synthetic fat and
tumbled for 15 minutes. 0.4% of formic acid (diluted with
water 1:10) and, after 45 minutes, 7% of a commercially
available chrome-tanning agent with 26% of chromium(III)
oxide and 33% ba~icity (according to Schorl-~mmer) are
added. After a further running time of 15 minutes, 3% of
fat (see above) is added. After 60 minutes, 3% of a
commercially available, sel f - basi f y i n g chromium-syntan
complex with 11% of chromium(III) oxide is added, and
running is continued for 150 minutes (pH = 3.7). The
liquor is heated to 38C, and 3% of a commercially
available chromium-syntan complex with 12% of chromium-
(III) oxide and, after a running time of 15 minute~, 6%
of a fat mixture of natural and synthetic fats are added,
and tanning i8 completed in 8 hours. The residual liquor
ha~ a chromium(III) oxide content of 0.9 g/l, a final pH
value of 3.6 and a final temperature of 36C.
In the usual manner, the leather is then neutrali~ed to
pH 6.5, fatted and finished via intermediate drying.
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Example 3
Production of furniture leather
For producing furniture leather, pelt3 limed, delimed and
bated as in Example la) are treated in a 50% liquor after
5 the addition of 8% of common salt with 0.5% of formic
acid (diluted with water 1:10) and 0.3% of Rulphuric acid
(diluted with water 1:10) and pickled for 120 minute~
(pickling p~ value 3.7).
10% of an aqueous solution (50% strength) of the conden-
sation product to be used according to the invention are
then added to the pickling liquor. After one hour, 1.5%
of a commercially available synthetic fat is added, and
tumbling is continued for 10 hourR. The final pH value i~
3.7 and the final temperature i3 32C. The residual
liquor i~ chromium-free. The wet-white~ are further
proce~Red analogously to Example la).
Exam~le 4
Production of furniture leather from un~plit pelts
For producing furniture leather, 100 kg of cow-hide pelts
limed in the usual manner are, in the unsplit ~tate,
initially washed twice for 15 minutes with 150% (relative
to pelt weight, like all percentage data below) of water
at 38C. The liquor i~ drained off and deliming is then
carried out for 60 minutes without liquor with 2.5% of
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ammonium sulphate, 0.3% of sodium bisulphite and 0.4% of
formic acid (diluted with water 1:10), 40~ of water at
35C is added, and bating is carried out with 0.5~ of a
commercially available bating agent (with 1500 tryptic
units) for 50 minutes (pH value of the liquor 7.5). The
cross-section of the pelts no longer gives any red
coloration with phenolphthalein.
Thi is followed by washing ~wice with 150% of water at
20C and the liquor i6 drained off except for a residual
liquor of about 30%. 5 minutes after the addition of 6%
of common salt, 0.5% of formic acid (diluted with water
1:10) and, after a further 10 minutes, 0.7% of sulphuric
acid (diluted with water 1:10) are added, and pickling is
carried out for 180 minut2s (pickling pH value 3.1).
8% of the condensation product to be used according to
the invention is then added to the pickling liquor, and
tumbling i8 continued for 10 hours. The final pH value i5
3.1 and the final temperature is 32C.
After draining off the residual liquor, the wet-whites
are unloaded, sammed and split to a thickne~s of 2 mm.
This gives about 400 g of chromium-free pelt shavings per
kg of pelt.
After 24 hours, the wet-whites are ~haved to 1 mm thick-
ness and further processed as in Example la). It is
necessary here, however, to take care that the pH value
in the chrome-tanning is raised to about 3.5 by adding
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lrl% (instead of 0.9%) of sodium bicarbonate.
Example 5
100 kg of cow hide pelts pretreated as in Example 4 are
pickled with 0.5% of formic acid (diluted with water
1:10) (pickling pH value 3.2). The pretreatment is
carried out with 17% of an aqueous solution (50~
strength) of the condensation product to be used accord-
inq to the invention. A6 in Example 4, the wet-whites are
then sammed, split and ~haved, and further processed as
in Example 2.
Example 6
Production of shoe upper leather
For producing shoe upper leather, 1000 kg of cow-hide
pelts limed in the usual manner (split to about 3.5 mm)
are initially waYhed in the tanning vessel with 150
(relative to pelt weight; like all percentage data below)
of water at 38C for 10 minutes. The liquor is drained
off and deliming i~ then carried out with 30% of water
at 35C with 2% of ammonium sulphate, 0.2% of sodium
bisulphite and 0.2% of formic acid (diluted with water
1:10) for 30 minutes, and bating is carried out for 30
minutes with 0.5% of a commercially available bating
agent (with 1500 tryptic unit~) (pH value of the liquor
8.3). The cros~-~ection of the pelt~ no longer gives any
red coloration with phenolphthalein. This i6 followed by
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washing twice with 150% of water at 20C and the liquor
is drained off except for a residual li~uor of about 20%.
5 minutes after the addition of 5% of common salt, O.5~
of formic acid (diluted with water 1:10) and, after 10
minutes, 0~7~ of sulphuric acid (diluted with water 1:10)
are added, and pickling i carried out for 60 minutes
(pickling pH value 3.1).
6% of the condensation product to be used according to
the invention and 0.1% of ~odium bisulphite (for elimin-
ating H2S) are then added to the pickling liquor. After1 hour, 1% of a commercially available natural fat (fish
oil product) i8 added, and tumbling is continued for 12
hours .
The final pH value iB 3.2 and the final temperature is
31C. After draining off the residual liquor, the wet-
whites are unloaded, 6ammed and, optionally after tem-
porary storage for 24 hourR, shaved to 1.8 mm thickne~s.
Thi~ gives about 36 kg of chromium-free shavings per 100
kg of pelt used.
100 kg of shaved wet-whites are treated in 150% (relative
to shaved weight; like all percentage data below) of
water at 35C with 12% of a commercially available,
weakly organic-masked chromium sulphate solution with 15%
of chromium(III) oxide and 40% basicity (according to
Schorlemmer) (pH ~ 3.1). After 2 hours, 3% of a commer-
cially available, self-basifjing chromium-syntan complex
with 11% of chromium~III) oxide i~ added, followed after
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2 hours (pH - 3.6) by heating to 39C.
After a running time of 12 hours, the liquor is drained
off, 100% of w~ter at 50C i~ added and rechroming i~
carried out for 60 minutes with 1.5% of a commercially
S available chrome-tanning agent with 26% of chromium(III)
oxide and 33~ basicity (according to Schor-lelnmer)and 2%
of the absvementioned chromium-~yntan complex (p~ 5 4.1).
Thi3 is followed by neutralisation with 1.5% of a com-
mercially available neutralisation tanning agent and 0.5~
of sodium bicarbonate to pH 4.7 and the liquor is drained
off after 45 minutes. The neutralised chrome leathers are
retanned in the conventional manner (with a combination
of replacement tanning agents, resin tanning agents or
polymer tanning agent~ and vegetable tanning agents),
dyed and fatted.
Example 7
Production of shoe upper leather
For producing shoe upper leather, 100 kg of cow-hide
pelts (split to about 3.5 mm) limed, delimed and bated
as in Example 6 are pickled for 60 minutes in 20% (rela-
tive to pelt weight, like all percentage data below) of
residual liquor after addition of 5% of common ~alt with
0.5% of formic acid (diluted with water 1:10) and 0.73 of
sulphuric acid ~diluted with water 1:10) (pickling pH
value 3.1).
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11% of an aqueous solution (50% strength) of the conden-
sation product to be used according to the invention and
0.1% of sodium bisulphite are then added to the pickling
liquor. As in Example 6, this i8 followed by fatting,
further tum~ling, unloading, samming and shaving.
50 kg of ~haved wet-whites are treated in 150% (relative
to shaved weight; like all percentage data below) of
water at 35C with 7% of a commercially available chrome-
tanning agent with 26~ of chromium(III) oxide and 33%
ba~icity (according to Schorl~miher)(pB = 3.0). After two
hours, 30% of a commercially available chromium-syntan
complex with 15% of chromium(III) oxide i~ added, and the
system is basified with 0.8% of sodium bicarbonate to pH
3.6. This i8 followed after 2 hour~ by heating to 39C~
The further processing and fini~hing of the leathers is
carried out a~ in Example 6.
Example 8
Production of furniture leather
For producing furniture leather, 800 kg of cow-hide pelts
(split to 2.1 mm) delimed and bated according to Example
1 are pickled in the tanning drum in 50% (relative to
pelt weight; like all percentage data below) of re~idual
liquor after addition of 7.5% of common salt and addition
0.4% of formic acid (diluted with water 1:10) after 5
minutes and of 0.5% of ~ulphuric acid after a further 10
minutes for a total of 180 minutes (pickling pH
Le A 28 634 - 19 -
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value 3.5).
4~ of the condensation product to be used according to
the invention i~ added to the pickling liquor. After 30
minutes, 0.5~ of a commercially available, synthetic
replacement tanning agent based on bis-(4-hydroxyphenyl)-
sulphone is added. After a further 60 minutes, 1.5% of a
commercially available synthetic fat is added, and
tumbling is continued for 12 hours.
The final p9 value is 3.5 and the final temperature is
33C.
After draining off the residual liquor, the wet-whites
are unloaded, sammed and, as in Example 1, shaved,
chrome-tanned and finished.
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